Bis-trialkylsilylphenoxysilanes



Patented Sept. 23, 1952 P er afi ntori j N1 OFFICE is miimy amnmoxrsams.13011111.. Speier; or; Pittsburgh, Pa., assignorto Dow CorningCorporation, Midland, .Mi'ch a' corporation of Michigan No; Drawing.Applicationrseptemberfls; 11-950,

Serial No. 185,515. In Great Britain Novem V This rmvention: relatestobisttrialkylsilylphensoxylvdialkylsilanes..Thecompounds.ofithis'inventionare usefulz-as intermediates in thepreparation of bis-phenyloldialkylsilanes. .Thelatter compounds areexcellent germicides and usefulin the preparation ofsilylpheno-l-formaldehyde resins.

This invention z'relate's to icompo-unds of the rbyp'e t -where R:is;-analkyl'radical, rR' isi alkyl-iori phenyl and chas aavaluefrom'flztol.- r

The above compounds are prepared by reacting a h'alophenoxysilaneof thetype :az silane: or thetype resin .andianralkalitmetal.

:In theseucompoun'dsX is a halogen atomiand 'Y is halogen or alkoxy.

'Thepro'ductsnf this inventionmayialsoibeipre- :pared by. reacting: abisehalophenoxysilane of the type . A ZIRIG with a silane of the typeRsSiY. In thisreaction .theLeX ecte'dI product SiRa 2 is not obtained. Arearrangement takes place to produce the bis trialkylsilylphenoxysilanesof this invention. The preparation of compounds of the formula isdisclosed in my copending application entitled Halophenoxysilanes,Serial Number 185,511, filed concurrently herewith.

The reaction is best carried out by adding a mixture of the two silanesto the molten alkali metal. Preferably sodium and potassium are used asthe metal. It has been found desirable to carry out the reaction in aninert solvent which will not react with sodium or the silanes.

Z8 iclainis. (Cl. 260448.8)

Such solvents should boil above the melting point .:of -,the':alka1imetal and includer f or. example; (tolsuene;.benzeneiand alkyhethersandsaturatedali- .phatic thydroearbons boiling above C.

.-After the reaction is complete' the reaction. mixture is filtered: anddistilled.

.-"-The.ha1ophenoxysilanes employed in thisQin- -ven'tlon: may or-maynot contain-a substituent hydrocarbon group. :Ithaszbeen foundz-that-theB group may be either saturated aliphatic radicals such as ethyl,methyl, "octadecyl and cyclohexylnrphenylradicals. 1 a

The rrdialkylsilanes may be'rteithertdiclrlorodialkylsilanesordialkyldiallroxysilanes wherein the .aalkyl'groups care .xfor:examplemethyl, iethyl or loctad'ecyl. :It is :preferredthat the-:silanenot contain both-achlorineiandranalkox-yiradical.

The above dialltylsilanes are well known, commercially availablematerials;

The "halophenoxysilanes z'ernplo'yed ln' this invention may be preparedby condensing :a halo- I phenol of the type H -withfia.ltrial-kylsilane'of the type RsSiY whei e Y ishalogen oralkoxy. In such casescondensation takes lace between the phenolic.ihydroxyl-xazid the sila'ne-Y 'gro-up to" produce the'plienoxy'si-lane and 'HCl or an alcohol.

The reaction is accomplished-by merely-mixing fth e two ingredients,however, "when 'orthoh'alophenols are employed, it is best to heattne.reaction mixture at a temperature" from"1"00 Ci"to 150 C. or toemploy-an HCl a'cceptorsuch as pyridine. 4

The compounds ofithis invention are useful as heat transfer media andther'nio expansion fluids.

The following examples are illustrative only. In the examples, Me is amethyl radical and Et an ethyl radical.

EXAMPLE 1 257 g. of p-chlorophenol, 217 g. of trimethylchlorosilane and156 g. of pyridine were mixed in toluene, cooled and filtered free ofpyridine hydrochloride. The filtrate contained -chlorophenoxytrimethylsilane. The filtrate was mixed with 129 g. ofdimethyldichlorosilane and the mixture was added to 92 g. of moltensodium in boiling toluene. A vigorous reaction occurred. When thereaction was completed, the mixture was filtered and distilled. Therewas obtained 46 g. of MezSi(p-MeaSiOCsH4-)2, boiling point 206 C. at mm.

3 EXAMPLE 2 Amixture o! 168 g. of

MeiSiOQCl and 52 g. of dichlorodimethylsilane was added to 43 g. ofmolten sodium in 200 cc. of boiling toluene. The reaction proceededrapidly and after its completion the reaction mixture wasfiltered' anddistilled. There was obtained a V V Me2Si[2-Me4 (M63810) CeH3-]2 boilingpoint 252 C. to 276 C. at 1 mm. This product was further identified byhydrolysisto.

EXAMPLE 3 v EXAMPLE 4 When a mixture of 276.5 grams of 2-phenyl-4-chlorophenoxytrimethylsilane and 64.5 grams of MezSiClz is reacted with46 grams of molten sodium'by the procedure'of Example 2, there isobtained as a reaction product the compound MBzSi [3-CsHs-4 (MezSiO)CaHa'l 2.

EXAMPLE 5 A- mixture was prepared of 1 molecular equivalent of'parabromophenyl and one equivalent of diethoxydimethylsilane. Themixture was heated to distillthe ethanol produced and the excessdiethoxydimethylsilane. There was thereby obtaineddimethylbis-parabromophenoxysilane. A mixture was prepared of 122 gramsof this compound and 65 grams of chlorotrimethylsilane. The mixture wasadded to 30 grams of molten sodium suspended in 200 cc. of boilingtoluene containing grams of chlorotrimethylsilane. The

mixture was refluxed for one-half hour, following which it wascooled'and filtered. Distillation of the reaction product gave theunexpected rearrangement product: MeZSi (p-CeH4OSiMes) 2.

' That which is claimed is: 1. Compounds of the formula K 1 OBiRs 1'halophenoxy dialkylsilane of the formula in whichR'represents an alkylradical, R is a radical selected from the group consisting of Aalkyl'and phenyl radicals, X is a halogen atom,

and c is an integer Of from 0 to 1 inclusive, with a 'silane of theformula' RsSiX'where Rand X are as above defined by contacting the twowith an alkali metal, whereby the rearrangement prod- 7. The methodwhich comprises reacting a'bishaiophenoxydialkylsilane of the formula inwhich R represents an alkyl radical, R is a radical selected from thegroup consisting of alkyl and phenyl radicals, X is a halogen atom, andc is an integer of from 0 to 1 inclusive, with a silane of the formulaRsSlX, where R and X are as above defined, by contacting the two inliquid phase with a molten alkali metal, whereby the rearrangementproduct da 4 osm:

is obtained.

8. The method in accordance with claim 7 wherein R represents a methylradical, X is selected from the group -c'ffr'isisting of chlorine andbromine atoms, and c equals 0.

' JOHN L. SPEIER, JR.

No references cited.

1. COMPOUNDS OF THE FORMULA